Cobalt deposition on barrier surfaces

ABSTRACT

Embodiments of the invention provide processes for depositing a cobalt layer on a barrier layer and subsequently depositing a conductive material, such as copper or a copper alloy, thereon. In one embodiment, a method for depositing materials on a substrate surface is provided which includes forming a barrier layer on a substrate, exposing the substrate to dicobalt hexacarbonyl butylacetylene (CCTBA) and hydrogen to form a cobalt layer on the barrier layer during a vapor deposition process (e.g., CVD or ALD), and depositing a conductive material over the cobalt layer. In some examples, the barrier layer and/or the cobalt layer may be exposed to a gas or a reagent during a treatment process, such as a thermal process, an in situ plasma process, or a remote plasma process.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. Ser. No. 12/111,923,filed Apr. 29, 2008 now abandoned and is a continuation-in-part of U.S.Ser. No. 12/111,930, filed Apr. 29, 2008, now abandoned which are bothcontinuation-in-parts of U.S. Ser. No. 11/733,929, filed Apr. 11, 2007,now U.S. Pat. No. 8,110,489 which are all herein incorporated byreference in their entirety. U.S. Ser. No. 11/733,929 claims benefit ofU.S. Ser. No. 60/791,366, filed Apr. 11, 2006, and U.S. Ser. No.60/863,939, filed Nov. 1, 2006, and is also a continuation-in-part ofU.S. Ser. No. 11/456,073, filed Jul. 6, 2006, and issued as U.S. Pat.No. 7,416,979, which is a continuation of U.S. Ser. No. 10/845,970,filed May 14, 2004, and now abandoned, which is a continuation of U.S.Ser. No. 10/044,412, filed Jan. 9, 2002, and issued as U.S. Pat. No.6,740,585, which is a continuation-in part of U.S. Ser. No. 09/916,234,filed Jul. 25, 2001, and now abandoned, which are all hereinincorporated by reference in their entirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

Embodiments of the invention generally relate to a metallization processfor manufacturing electronic and semiconductor devices, moreparticularly, embodiments relate to a method for depositing a cobaltlayer on a barrier layer before depositing a conductive layer or contactmaterial thereon.

2. Description of the Related Art

Copper is the current metal of choice for use in multilevelmetallization processes that are crucial to device manufacturing. Themultilevel interconnects that drive the manufacturing processes requireplanarization of high aspect ratio apertures including contacts, vias,lines, and other features. Filling the features without creating voidsor deforming the feature geometry is more difficult when the featureshave higher aspect ratios. Reliable formation of interconnects is alsomore difficult as manufacturers strive to increase circuit density andquality.

As the use of copper has permeated the marketplace because of itsrelative low cost and processing properties, semiconductor manufacturerscontinue to look for ways to improve the boundary regions between copperand dielectric material by reducing copper diffusion and dewetting.Several processing methods have been developed to manufacture copperinterconnects as feature sizes have decreased. Each processing methodmay increase the likelihood of errors such as copper diffusion acrossboundary regions, copper crystalline structure deformation, anddewetting. Physical vapor deposition (PVD), chemical vapor deposition(CVD), atomic layer deposition (ALD), electrochemical plating (ECP),electroless deposition, chemical mechanical polishing (CMP),electrochemical mechanical polishing (ECMP), and other methods ofdepositing and removing copper layers utilize mechanical, electrical, orchemical methods to manipulate the copper that forms the interconnects.Barrier and capping layers may be deposited to contain the copper.

In the past, a layer of tantalum, tantalum nitride, or copper alloy withtin, aluminum, or magnesium was used to provide a barrier layer or anadhesion promoter between copper and other materials. These options areusually costly and are only partially effective. As the copper atomsalong the boundary regions experience changes in temperature, pressure,atmospheric conditions, or other process variables common duringmultiple step semiconductor processing, the copper may migrate along theboundary regions and become agglomerated copper. The copper may also beless uniformly dispersed along the boundary regions and become dewettedcopper. These changes in the boundary region include stress migrationand electromigration of the copper atoms. The stress migration andelectromigration of copper across the dielectric layers or otherstructures increases the resistivity of the resulting structures andreduces the reliability of the resulting devices.

Therefore, a need exists to enhance the stability and adhesion of aconductive layer or a contact material on a barrier layer. Also, a needexists to improve the electromigration reliability of acopper-containing layer, especially for copper line formations, whilepreventing the diffusion of copper into neighboring materials, such asdielectric materials.

SUMMARY OF THE INVENTION

Embodiments of the invention provide processes for depositing a cobaltlayer on a barrier layer prior to depositing a conductive layer thereon.In one embodiment, a method for depositing materials on a substratesurface is provided which includes forming a barrier layer on asubstrate, exposing the substrate to dicobalt hexacarbonylbutylacetylene (CCTBA) and hydrogen (H₂) to form a cobalt layer on thebarrier layer during a vapor deposition process, and depositing aconductive material over the cobalt layer.

In one example, the substrate may be exposed to a deposition gascontaining CCTBA and hydrogen during a thermal CVD process. In anotherexample, the substrate may be sequentially exposed to CCTBA and hydrogenduring an ALD process. The substrate may be heated to a temperaturewithin a range from about 100° C. to about 250° C. during the CVD or ALDprocess. The cobalt layer may be deposited with a thickness of less thanabout 40 Å.

In some examples, the barrier layer and/or the cobalt layer may beexposed to a gas or a reagent during a treatment process. The treatmentmay be a thermal process, an in situ plasma process, or a remote plasmaprocess. The gas or the reagent may contain or be nitrogen (N₂), ammonia(NH₃), hydrogen (H₂), an ammonia/hydrogen mixture, silane, disilane,helium, argon, plasmas thereof, derivatives thereof, or combinationsthereof. The barrier layer or the cobalt layer may be exposed to thegas, reagent, or plasma for a time period within a range from about 1second to about 30 seconds. The substrate may be heated to a temperaturewithin a range from about 50° C. to about 400° C. during the treatmentprocess.

In some examples, the conductive material may contain copper or a copperalloy. The conductive material may contain a seed layer and a bulklayer. Alternatively, the conductive material may be directly depositedon the cobalt layer, such as by an electrochemical plating (ECP)process. In one example, a seed layer containing copper may be depositedby a PVD process or a CVD process. In another example, the bulk layercontains copper and may be deposited by an ECP process. The barrierlayer may contain tantalum, tantalum nitride, titanium, titaniumnitride, tungsten, tungsten nitride, alloys thereof, derivativesthereof, or combinations thereof. In one example, the barrier layer maybe a tantalum nitride layer disposed on a tantalum layer.

In another embodiment, a method for depositing materials on a substratesurface is provided which includes forming a barrier layer on asubstrate, exposing the barrier layer to a first plasma during apre-treatment process, exposing the substrate to CCTBA and hydrogen toform a cobalt layer on the barrier layer during a vapor depositionprocess, exposing the cobalt layer to a second plasma during apost-treatment process, and depositing a copper layer on the cobaltlayer by a vapor deposition process, such as a PVD process or a CVDprocess.

In another embodiment, a method for depositing materials on a substratesurface is provided which includes forming a barrier layer on asubstrate, exposing the barrier layer to a plasma during a pre-treatmentprocess, exposing the substrate to CCTBA and a reducing gas to form acobalt layer on the barrier layer during a vapor deposition process,exposing the cobalt layer to a hydrogen plasma during a post-treatmentprocess, and depositing a copper material over the cobalt layer. In oneexample, the vapor deposition process to deposit the cobalt layer andthe post-treatment process are sequentially repeated to form a cobaltmaterial. The cobalt material contains multiple cobalt layers which haveeach been exposed to a hydrogen plasma prior to having another cobaltlayer deposited thereon.

BRIEF DESCRIPTION OF THE DRAWINGS

So that the manner in which the above recited features of the inventioncan be understood in detail, a more particular description of theinvention, briefly summarized above, may be had by reference toembodiments, some of which are illustrated in the appended drawings. Itis to be noted, however, that the appended drawings illustrate onlytypical embodiments of this invention and are therefore not to beconsidered limiting of its scope, for the invention may admit to otherequally effective embodiments.

FIG. 1 depicts a flow chart illustrating a process according to anembodiment described herein; and

FIGS. 2A-2F depict schematic views of a substrate at different processsteps according to an embodiment described herein.

DETAILED DESCRIPTION

Embodiments of the invention provide a method for depositing a cobaltlayer on a barrier layer or layer prior to depositing a conductive layerthereon. The cobalt layer and barrier layer may each optionally beexposed to a treatment process, such as a plasma process or a thermalprocess. The conductive layer may contain copper or a copper alloy andbe deposited by a physical vapor deposition (PVD) process, an atomiclayer deposition (ALD) process, an electrochemical plating (ECP)process, or an electroless deposition process. The cobalt layer improvescopper boundary region properties to promote adhesion, improve gapfilland electromigration performance, decrease diffusion and agglomeration,and encourage uniform roughness and wetting of the substrate surfaceduring processing.

FIG. 1 depicts a flow chart illustrating process 100 according to anembodiment of the invention. Process 100 may be used to form aninterconnect or other device on a substrate. In one embodiment, steps110-150 of process 100 may be performed on substrate 200, depicted inFIGS. 2A-2F. Process 100 includes depositing or forming a barrier layeron a substrate (step 110), optionally exposing the barrier layer to apre-treatment process (step 120), depositing a cobalt layer on thebarrier layer (step 130), optionally exposing the cobalt layer to apost-treatment process (step 140), and depositing at least oneconductive layer on the cobalt layer (step 150).

FIG. 2A depicts substrate 200 containing dielectric layer 204 disposedover underlayer 202. Aperture 206 is formed within dielectric layer 204and may be a via, damascene, trough, or other passageway formed therein.Underlayer 202 may be a substrate, substrate surface, contact layer, oranother layer depending on device structure. Dielectric layer 204 maycontain a dielectric material, such as a low-k dielectric material. Inone example, dielectric layer 204 contains a low-k dielectric material,such as a silicon carbide oxide material, or a carbon doped siliconoxide material, for example, BLACK DIAMOND® II low-k dielectricmaterial, available from Applied Materials, Inc., located in SantaClara, Calif. Another example of a suitable material for dielectriclayer 204 is a silicon carbide based film formed using chemical vapordeposition (CVD) or plasma enhanced CVD (PE-CVD) processes such asdescribed in commonly assigned U.S. Pat. Nos. 6,537,733, 6,790,788, and6,890,850, which are incorporated herein by reference.

In one embodiment, at least one barrier layer or material may bedeposited or formed on a substrate during step 110 of process 100. Inone example, FIG. 2B depicts barrier layer 210 disposed on substrate200, over dielectric layer 204, and conformally within aperture 206.Barrier layer 210 may be one layer or multiple layers. Barrier layer 210may contain titanium, titanium nitride, tantalum, tantalum nitride,tungsten, tungsten nitride, silicides thereof, derivatives thereof, orcombinations thereof. In some embodiments, barrier layer 210 may containa bilayer of tantalum/tantalum nitride, titanium/titanium nitride, ortungsten/tungsten nitride. Barrier layer 210 may have a thickness withina range from about 5 Å to about 50 Å, preferably, from about 10 Å toabout 30 Å, and may be formed or deposited by PVD, ALD, plasma enhancedALD (PE-ALD), CVD, PE-CVD, pulsed-CVD, or combinations thereof.

In one example, barrier layer 210 contains a lower layer of metallictantalum deposited by a PVD process and an upper layer disposed over thelower layer of tantalum nitride layer deposited by another PVD process.In another example, barrier layer 210 contains a lower layer of metallictantalum deposited by an ALD process and an upper layer disposed overthe lower layer of tantalum nitride layer deposited by a CVD process. Inanother example, barrier layer 210 contains a lower layer of metallictantalum deposited by a PVD process and an upper layer disposed over thelower layer of tantalum nitride layer deposited by a CVD process.

For example, barrier layer 210 may contain tantalum nitride depositedusing a CVD process or an ALD process wherein tantalum-containingcompound or tantalum precursor (e.g., PDMAT) and nitrogen precursor(e.g., ammonia) are reacted. In one embodiment, tantalum and/or tantalumnitride is deposited as barrier layer 210 by an ALD process as describedin commonly assigned U.S. Ser. No. 10/281,079, filed Oct. 25, 2002, andpublished as US 2003-0121608, which is herein incorporated by reference.In one example, a Ta/TaN bilayer may be deposited as barrier layer 210,such as a metallic tantalum layer and a tantalum nitride layer that areindependently deposited by ALD, CVD, and/or PVD processes, one layer ontop of the other layer, in either order.

In another example, a Ti/TiN bilayer may be deposited as barrier layer210, such as a metallic titanium layer and a titanium nitride layer thatare independently deposited by ALD, CVD, and/or PVD processes, one layeron top of the other layer, in either order. In another example, a W/WNbilayer may be deposited as barrier layer 210, such as a metallictungsten layer and a tungsten nitride layer that are independentlydeposited by ALD, CVD, and/or PVD processes, one layer on top of theother layer, in either order.

At step 120, barrier layer 210 may be optionally exposed to apre-treatment process, such as a plasma process or a thermal process.Process gases and/or reagents that may be exposed to substrate 200during plasma or thermal pre-treatment processes include hydrogen (e.g.,H₂ or atomic-H), nitrogen (e.g., N₂ or atomic-N), ammonia (NH₃), ahydrogen and ammonia mixture (H₂/NH₃), hydrazine (N₂H₄), silane (SiH₄),disilane (Si₂H₆), helium, argon, derivatives thereof, plasmas thereof,or combinations thereof. The process gas may flow into the processingchamber or be exposed to the substrate having a flow rate within a rangefrom about 500 sccm to about 10 slm, preferably, from about 1 slm toabout 6 slm, for example, about 3 slm.

In one embodiment, substrate 200 and barrier layer 210 may be exposed toa plasma to remove contaminants from barrier layer 210 during thepre-treatment process at step 120. Substrate 200 may be positionedwithin a processing chamber and exposed to a process gas which isignited to form the plasma. The process gas may contain one gaseouscompound or multiple gaseous compounds. Substrate 200 may be at roomtemperature (e.g., 23° C.), but is usually preheated to the desiredtemperature of the subsequent deposition process. Substrate 200 may beheated to a temperature within a range from about 100° C. to about 400°C., preferably, from about 125° C. to about 350° C., and morepreferably, from about 150° C. to about 300° C., such as about 200° C.or about 250° C.

The processing chamber may produce an in situ plasma or be equipped witha remote plasma source (RPS). In one embodiment, substrate 200 may beexposed to the plasma (e.g., in situ or remotely) for a time periodwithin a range from about 0.5 seconds to about 90 seconds, preferably,from about 10 seconds to about 60 seconds, and more preferably, fromabout 20 seconds to about 40 seconds. The plasma may be produced at apower within a range from about 100 watts to about 1,000 watts,preferably, from about 200 watts to about 600 watts, and morepreferably, from about 300 watts to about 500 watts. The processingchamber usually has an internal pressure of about 100 Torr or less, suchas within a range from about 0.1 Torr to about 100 Torr, preferably,from about 0.5 Torr to about 50 Torr, and more preferably, from about 1Torr to about 10 Torr.

In one example, substrate 200 and barrier layer 210 may be exposed to aplasma generated from hydrogen, ammonia, nitrogen, or mixtures thereof.In another example, substrate 200 and barrier layer 210 may be exposedto a plasma generated from hydrogen and ammonia. In another example,substrate 200 and barrier layer 210 may be exposed to a plasma generatedfrom hydrogen, nitrogen, silane, disilane, or mixtures thereof. Inanother example, substrate 200 and barrier layer 210 may be exposed to aplasma generated from hydrogen, nitrogen, argon, helium, or mixturesthereof.

In another embodiment, substrate 200 and barrier layer 210 are exposedto a process gas to remove contaminants from barrier layer 210 during athermal pre-treatment process at step 120. The thermal pre-treatmentprocess may be a rapid thermal process (RTP) or a rapid thermalannealing (RTA) process. Substrate 200 may be positioned within aprocessing chamber and exposed to at least one process gas and/orreagent. The processing chamber may be a deposition chamber that will beused for a subsequent deposition process, such as a PVD chamber, a CVDchamber, or an ALD chamber. Alternatively, the processing chamber may bea thermal annealing chamber, such as the RADIANCE® RTA chamber,commercially available from Applied Materials, Inc., Santa Clara, Calif.Substrate 200 may be heated to a temperature within a range from about25° C. to about 800° C., preferably, from about 50° C. to about 400° C.,and more preferably, from about 100° C. to about 300° C. Substrate 200may be heated for a time period within a range from about 2 minutes toabout 20 minutes, preferably, from about 5 minutes to about 15 minutes.For example, substrate 200 may be heated to about 400° C. for about 12minutes within the processing chamber.

In one example, substrate 200 and barrier layer 210 may be exposed tohydrogen, ammonia, nitrogen, or mixtures thereof while being heatedwithin the processing chamber. In another example, substrate 200 andbarrier layer 210 may be exposed to an ammonia/hydrogen mixture whilebeing heated within the processing chamber. In another example,substrate 200 and barrier layer 210 may be exposed to hydrogen,nitrogen, silane, disilane, or mixtures thereof while being heatedwithin the processing chamber. In another example, substrate 200 andbarrier layer 210 may be exposed to hydrogen, nitrogen, argon, helium,or mixtures thereof while being heated within the processing chamber.

In another embodiment, at least cobalt material or layer may bedeposited or formed on the substrate during step 130 of process 100. Inone example, FIG. 2C depicts cobalt layer 220 disposed on substrate 200,over barrier layer 210, and conformally within aperture 206. Cobaltlayer 220 is usually a single layer, but may contain multiple layers.Cobalt layer 220 may be a continuous layer or a discontinuous layeracross barrier layer 210. Cobalt layer 220 may have a thickness of about40 Å or less, such as within a range from about 2 Å to about 40 Å,preferably, from about 5 Å to about 30 Å. Cobalt layer 220 may be formedor deposited by a vapor deposition process, such as CVD, PE-CVD,pulsed-CVD, ALD, PE-ALD, or PVD. The plasma enhanced vapor depositionprocess, namely PE-CVD and PE-ALD, may be an in situ plasma processwithin the processing chamber or may be a remote plasma process suchthat a plasma is ignited in by a RPS and directed into the processingchamber. In many examples, cobalt layer 220 contains metallic cobalt.Alternatively, in other examples, cobalt layer 220 may contain one ormore cobalt materials, such as metallic cobalt, cobalt silicide, cobaltboride, cobalt phosphide, alloys thereof, derivatives thereof, orcombinations thereof.

In some embodiments, cobalt layer 220 may be formed or deposited bysimultaneously introducing a cobalt precursor and a reagent into theprocessing chamber during a thermal CVD process, a pulsed-CVD process, aPE-CVD process, or a pulsed PE-CVD process. In other embodiments, thecobalt precursor may be introduced into the processing chamber without areagent during a thermal CVD process, a pulsed-CVD process, a PE-CVDprocess, or a pulsed PE-CVD process. Alternatively, in otherembodiments, cobalt layer 220 may be formed or deposited by sequentiallyintroducing a cobalt precursor and a reagent into the processing chamberduring a thermal ALD process or a PE-ALD process.

Cobalt layer 220 may contain metallic cobalt in some examples, but maycontain other cobalt materials in other examples. Suitable cobaltprecursors for forming cobalt materials (e.g., metallic cobalt or cobaltalloys) by CVD or ALD processes described herein include cobalt carbonylcomplexes, cobalt amidinates compounds, cobaltocene compounds, cobaltdienyl complexes, cobalt nitrosyl complexes, derivatives thereof,complexes thereof, plasmas thereof, or combinations thereof. In someembodiments, cobalt materials may be deposited by CVD and ALD processesfurther described in commonly assigned U.S. Pat. Nos. 7,264,846 and7,404,985, which are herein incorporated by reference.

In some embodiments, cobalt carbonyl compounds or complexes may beutilized as cobalt precursors. Cobalt carbonyl compounds or complexeshave the general chemical formula (CO)_(x)Co_(y)L_(z), where X may be 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, Y may be 1, 2, 3, 4, or 5, and Zmay be 1, 2, 3, 4, 5, 6, 7, or 8. The group L is absent, one ligand ormultiple ligands, that may be the same ligand or different ligands, andinclude cyclopentadienyl, alkylcyclopentadienyl (e.g.,methylcyclopentadienyl or pentamethylcyclopentadienyl), pentadienyl,alkylpentadienyl, cyclobutadienyl, butadienyl, ethylene, allyl (orpropylene), alkenes, dialkenes, alkynes, acetylene, butylacetylene,nitrosyl, ammonia, derivatives thereof, complexes thereof, plasmasthereof, or combinations thereof.

In one embodiment, dicobalt hexacarbonyl acetyl compounds may be used toform cobalt materials (e.g., cobalt layer 220) during a depositionprocess. Dicobalt hexacarbonyl acetyl compounds may have the chemicalformula of (CO)₆CO₂(RC≡CR′), wherein R and R′ are independently selectedfrom hydrogen, methyl, ethyl, propyl, isopropyl, butyl, tertbutyl,penta, benzyl, aryl, isomers thereof, derivatives thereof, orcombinations thereof. In one example, dicobalt hexacarbonylbutylacetylene (CCTBA, (CO)₆CO₂(HC≡C^(t)Bu)) is the cobalt precursor.Other examples of dicobalt hexacarbonyl acetyl compounds includedicobalt hexacarbonyl methylbutylacetylene ((CO)₆CO₂(MeC≡C^(t)Bu)),dicobalt hexacarbonyl phenylacetylene ((CO)₆CO₂(HC≡CPh)), hexacarbonylmethylphenylacetylene ((CO)₆CO₂(MeC≡CPh)), dicobalt hexacarbonylmethylacetylene ((CO)₆CO₂(HC≡CMe)), dicobalt hexacarbonyldimethylacetylene ((CO)₆CO₂(MeC≡CMe)), derivatives thereof, complexesthereof, plasmas thereof, or combinations thereof. Other exemplarycobalt carbonyl complexes include cyclopentadienyl cobalt bis(carbonyl)(CpCo(CO)₂), tricarbonyl allyl cobalt ((CO)₃Co(CH₂CH═CH₂)), derivativesthereof, complexes thereof, plasmas thereof, or combinations thereof.

In another embodiment, cobalt amidinates or cobalt amido complexes maybe utilized as cobalt precursors. Cobalt amido complexes have thegeneral chemical formula (RR′N)_(x)Co, where X may be 1, 2, or 3, and Rand R′ are independently hydrogen, methyl, ethyl, propyl, butyl, alkyl,silyl, alkylsilyl, derivatives thereof, or combinations thereof. Someexemplary cobalt amido complexes includebis(di(butyldimethylsilyl)amido) cobalt (((BuMe₂Si)₂N)₂Co),bis(di(ethyldimethylsilyl)amido) cobalt (((EtMe₂Si)₂N)₂Co),bis(di(propyldimethylsilyl)amido) cobalt (((PrMe₂Si)₂N)₂Co),bis(di(trimethylsilyl)amido) cobalt (((Me₃Si)₂N)₂Co),tris(di(trimethylsilyl)amido) cobalt (((Me₃Si)₂N)₃Co), derivativesthereof, complexes thereof, plasmas thereof, or combinations thereof.

Some exemplary cobalt precursors include methylcyclopentadienyl cobaltbis(carbonyl) (MeCpCo(CO)₂), ethylcyclopentadienyl cobalt bis(carbonyl)(EtCpCo(CO)₂), pentamethylcyclopentadienyl cobalt bis(carbonyl) (Me₅CpCo(CO)₂), dicobalt octa(carbonyl) (CO₂(CO)₈), nitrosyl cobalttris(carbonyl) ((ON)Co(CO)₃), bis(cyclopentadienyl) cobalt,(cyclopentadienyl) cobalt (cyclohexadienyl), cyclopentadienyl cobalt(1,3-hexadienyl), (cyclobutadienyl) cobalt (cyclopentadienyl),bis(methylcyclopentadienyl) cobalt, (cyclopentadienyl) cobalt(5-methylcyclopentadienyl), bis(ethylene) cobalt(pentamethylcyclopentadienyl), cobalt tetracarbonyl iodide, cobalttetracarbonyl trichlorosilane, carbonyl chloridetris(trimethylphosphine) cobalt, cobalttricarbonyl-hydrotributylphosphine, acetylene dicobalt hexacarbonyl,acetylene dicobalt pentacarbonyl triethylphosphine, derivatives thereof,complexes thereof, plasmas thereof, or combinations thereof.

In some examples, alternative reagents, including reducing agents, maybe used to react with cobalt precursors while forming cobalt materials(e.g., metallic cobalt or cobalt alloys) by processes described hereininclude hydrogen (e.g., H₂ or atomic-H), nitrogen (e.g., N₂ oratomic-N), ammonia (NH₃), hydrazine (N₂H₄), a hydrogen and ammoniamixture (H₂/NH₃), borane (BH₃), diborane (B₂H₆), triethylborane (Et₃B),silane (SiH₄), disilane (Si₂H₆), trisilane (Si₃H₈), tetrasilane(Si₄H₁₀), methyl silane (SiCH₆), dimethylsilane (SiC₂H₈), phosphine(PH₃), derivatives thereof, plasmas thereof, or combinations thereof.

In one embodiment, cobalt layer 220 containing metallic cobalt isdeposited by simultaneously exposing substrate 200 to a cobalt precursorgas and a reducing agent during a thermal CVD process. In an alternativeembodiment, cobalt layer 220 containing metallic cobalt is deposited bysimultaneously exposing substrate 200 to a cobalt precursor gas and areducing agent gas during a plasma enhanced CVD process. The plasmasource may be an in situ plasma source within the CVD chamber or a RPSpositioned outside of the CVD chamber. The cobalt precursor gas may beformed by passing a carrier gas (e.g., nitrogen or argon) through anampoule of a cobalt precursor (e.g., CCTBA). The reducing agent gas maybe a single compound (e.g., H₂), and therefore have no carrier gas.Alternatively, the reducing agent gas may be formed by passing a carriergas through an ampoule of a reducing agent.

The ampoule may be heated depending on the cobalt precursor or reducingagent used during the process. In one example, an ampoule containing acobalt precursor, such as a dicobalt hexacarbonyl acetyl compound orother cobalt carbonyl compound (e.g., (CO)_(x)Co_(y)L_(z)) may be heatedto a temperature within a range from about 30° C. to about 500° C. Thecobalt precursor gas usually has a flow rate within a range from about100 sccm (standard cubic centimeters per minute) to about 2,000 sccm,preferably, from about 200 sccm to about 1,000 sccm, and morepreferably, from about 300 sccm to about 700 sccm, for example, about500 sccm. The reducing agent gas usually has a flow rate within a rangefrom about 0.5 slm (standard liters per minute) to about 10 slm,preferably, from about 1 slm to about 8 slm, and more preferably, fromabout 2 slm to about 6 slm. In one example, reducing agent gas ishydrogen and has a flow rate within a range from about 2 slm to about 6slm, such as about 4 slm.

The cobalt precursor gas and the reducing agent gas may be combined toform a deposition gas prior to, while, or subsequent to entering theprocessing chamber during a deposition process to deposit cobalt layer220. Substrate 200 may be positioned within a processing chamber andheated to a temperature within a range from about 25° C. to about 800°C., preferably, from about 50° C. to about 400° C., and more preferably,from about 100° C. to about 250° C., such as about 150° C. Once at apredetermined temperature, substrate 200 may be exposed to thedeposition gas containing the cobalt precursor gas and the reducingagent gas for a time period within a range from about 0.1 seconds toabout 120 seconds, preferably, from about 1 second to about 60 seconds,and more preferably, from about 5 seconds to about 30 seconds. Forexample, substrate 200 may be heated to about 150° C. for about 10minutes within the processing chamber while forming cobalt layer 220during the CVD process.

At step 140, cobalt layer 220 may be optionally exposed to apost-treatment process, such as a plasma process or a thermal process.Process gases and/or reagents that may be exposed to substrate 200 andcobalt layer 220 during plasma or thermal post-treatment processesinclude hydrogen (e.g., H₂ or atomic-H), nitrogen (e.g., N₂ oratomic-N), ammonia (NH₃), a hydrogen and ammonia mixture (H₂/NH₃),hydrazine (N₂H₄), silane (SiH₄), disilane (Si₂H₆), helium, argon,derivatives thereof, plasmas thereof, or combinations thereof. Theprocess gas may flow into the processing chamber or be exposed to thesubstrate having a flow rate within a range from about 500 sccm to about10 slm, preferably, from about 1 slm to about 6 slm, for example, about3 slm.

In one embodiment, substrate 200 and cobalt layer 220 are exposed to aplasma to remove contaminants from cobalt layer 220 during thepost-treatment process at step 140. Substrate 200 may be positionedwithin a processing chamber and exposed to a process gas which isignited to form the plasma. The process gas may contain one gaseouscompound or multiple gaseous compounds. Substrate 200 may be at roomtemperature (e.g., 23° C.), but is usually preheated to the desiredtemperature of the subsequent deposition process. Substrate 200 may beheated to a temperature within a range from about 100° C. to about 400°C., preferably, from about 125° C. to about 350° C., and morepreferably, from about 150° C. to about 300° C., such as about 200° C.or about 250° C.

The processing chamber may produce an in situ plasma or be equipped witha RPS. In one embodiment, substrate 200 may be exposed to the plasma(e.g., in situ or remotely) for a time period within a range from about0.5 seconds to about 90 seconds, preferably, from about 10 seconds toabout 60 seconds, and more preferably, from about 20 seconds to about 40seconds. The plasma may be produced at a power within a range from about100 watts to about 1,000 watts, preferably, from about 200 watts toabout 600 watts, and more preferably, from about 300 watts to about 500watts. The processing chamber usually has an internal pressure of about100 Torr or less, such as within a range from about 0.1 Torr to about100 Torr, preferably, from about 0.5 Torr to about 50 Torr, and morepreferably, from about 1 Torr to about 10 Torr.

In one example, substrate 200 and cobalt layer 220 may be exposed to aplasma generated from hydrogen, ammonia, nitrogen, or mixtures thereof.In another example, substrate 200 and cobalt layer 220 may be exposed toa plasma generated from hydrogen and ammonia. In another example,substrate 200 and cobalt layer 220 may be exposed to a plasma generatedfrom hydrogen, nitrogen, silane, disilane, or mixtures thereof. Inanother example, substrate 200 and cobalt layer 220 may be exposed to aplasma generated from hydrogen, nitrogen, argon, helium, or mixturesthereof.

In some examples, substrate 200 and cobalt layer 220 may be exposed to ahydrogen plasma generated from hydrogen gas ignited by a RPS. Cobaltlayer 220 may be exposed to hydrogen gas with a flow rate within a rangefrom about 2 slm to about 4 slm. The processing chamber may have aninternal pressure within a range from about 1 Torr to about 10 Torr, andthe plasma is ignited by a RPS having a power within a range from about300 watts to about 500 watts. In one embodiment, the plasma may beexposed to cobalt layer 220 for a time period within a range from about20 seconds to about 40 seconds for every deposited layer of cobaltmaterial having a thickness within a range from about 7 Å to about 10 Å.Multiple treatments may be performed sequentially with the multiplelayers of deposited cobalt material while forming cobalt layer 220.

In another embodiment, substrate 200 and cobalt layer 220 are exposed toa process gas to remove contaminants from cobalt layer 220 during athermal post-treatment process at step 140. The thermal post-treatmentprocess may be a RTP or a RTA process. Substrate 200 may be positionedwithin a processing chamber and exposed to at least one process gasand/or reagent. The processing chamber may be a deposition chamber thatwas used in a prior deposition process or will be used for a subsequentdeposition process, such as a PVD chamber, a CVD chamber, or an ALDchamber. Alternatively, the processing chamber may be a thermalannealing chamber, such as the RADIANCE® RTA chamber, commerciallyavailable from Applied Materials, Inc., Santa Clara, Calif. Substrate200 may be heated to a temperature within a range from about 25° C. toabout 800° C., preferably, from about 50° C. to about 400° C., and morepreferably, from about 100° C. to about 300° C. Substrate 200 may beheated for a time period within a range from about 2 minutes to about 20minutes, preferably, from about 5 minutes to about 15 minutes. Forexample, substrate 200 may be heated to about 400° C. for about 12minutes within the processing chamber.

In one example, substrate 200 and cobalt layer 220 may be exposed tohydrogen, ammonia, nitrogen, or mixtures thereof while being heatedwithin the processing chamber. In another example, substrate 200 andcobalt layer 220 may be exposed to an ammonia/hydrogen mixture whilebeing heated within the processing chamber. In another example,substrate 200 and cobalt layer 220 may be exposed to hydrogen, nitrogen,silane, disilane, or mixtures thereof while being heated within theprocessing chamber. In another example, substrate 200 and cobalt layer220 may be exposed to hydrogen, nitrogen, argon, helium, or mixturesthereof while being heated within the processing chamber.

FIG. 2C depicts aperture 206 formed within dielectric layer 204 onsubstrate 200. Aperture 206 contains barrier layer 210 and cobalt layer220 conformally disposed therein. In another embodiment, during step 150of process 100, a conductive layer may be deposited or formed on or overcobalt layer 220. In one embodiment, the conductive layer is bulk layer240 which may be directly deposited over cobalt layer 220, as depictedin FIG. 2D. Alternatively, in another embodiment, the conductive layeris seed layer 230 and bulk layer 240. Seed layer 230 may be depositedover cobalt layer 220 and subsequently, bulk layer 240 may be depositedover seed layer 230, as depicted in FIGS. 2E-2F.

Seed layer 230 and bulk layer 240 may be deposited or formed during asingle deposition process or multiple deposition processes. Seed layer230 may contain copper, tungsten, aluminum, ruthenium, cobalt, silver,platinum, palladium, alloys thereof, derivatives thereof or combinationsthereof. Bulk layer 240 may contain copper, tungsten, aluminum, alloysthereof, derivatives thereof or combinations thereof. Usually, seedlayer 230 and bulk layer 240 may independently contain copper, tungsten,aluminum, alloys thereof, derivatives thereof or combinations thereof.Seed layer 230 and bulk layer 240 may independently be deposited byusing one or more deposition process, such as a CVD process, an ALDprocess, a PVD process, an electroless deposition process, an ECPprocess, derivatives thereof, or combinations thereof.

In one example, each of seed layer 230 and bulk layer 240 containscopper or a copper alloy. For example, seed layer 230 containing coppermay be formed on cobalt layer 220 by a PVD process and thereafter, bulklayer 240 containing copper may be deposited to fill aperture 206 by anECP process or an electroless deposition process. In another example,seed layer 230 containing copper may be formed on cobalt layer 220 by anALD process and thereafter, bulk layer 240 containing copper may bedeposited to fill aperture 206 by an ECP process or an electrolessdeposition process. In another example, seed layer 230 containing coppermay be formed on cobalt layer 220 by a CVD process and thereafter, bulklayer 240 containing copper may be deposited to fill aperture 206 by anECP process or an electroless deposition process. In another example,seed layer 230 containing copper may be formed on cobalt layer 220 by anelectroless process and thereafter, bulk layer 240 containing copper maybe deposited to fill aperture 206 by an ECP process or an electrolessdeposition process. In another example, cobalt layer 220 serves as aseed layer to which bulk layer 240 containing copper may be directlydeposited to fill aperture 206 by an ECP process or an electrolessdeposition process.

In one example, each of seed layer 230 and bulk layer 240 containstungsten or a tungsten alloy. For example, seed layer 230 containingtungsten may be formed on cobalt layer 220 by a PVD process andthereafter, bulk layer 240 containing tungsten may be deposited to fillaperture 206 by a CVD process or a pulsed-CVD process. In anotherexample, seed layer 230 containing tungsten may be formed on cobaltlayer 220 by an ALD process and thereafter, bulk layer 240 containingtungsten may be deposited to fill aperture 206 by a CVD process or apulsed-CVD process. In another example, seed layer 230 containingtungsten may be formed on cobalt layer 220 by a pulsed-CVD process andthereafter, bulk layer 240 containing tungsten may be deposited to fillaperture 206 by a CVD process or a pulsed-CVD process. In anotherexample, seed layer 230 containing tungsten may be formed on cobaltlayer 220 by an electroless process and thereafter, bulk layer 240containing tungsten may be deposited to fill aperture 206 by a CVDprocess or a pulsed-CVD process. In another example, cobalt layer 220serves as a seed layer to which bulk layer 240 containing tungsten maybe directly deposited to fill aperture 206 by a CVD process or apulsed-CVD process.

An ALD processing chamber used during embodiments described herein isavailable from Applied Materials, Inc., located in Santa Clara, Calif. Adetailed description of an ALD processing chamber may be found incommonly assigned U.S. Pat. Nos. 6,916,398 and 6,878,206, commonlyassigned U.S. Ser. No. 10/281,079, filed on Oct. 25, 2002, and publishedas U.S. Pub. No. 2003-0121608, and commonly assigned U.S. Ser. Nos.11/556,745, 11/556,752, 11/556,756, 11/556,758, 11/556,763, each filedNov. 6, 2006, and published as U.S. Pub. Nos. 2007-0119379,2007-0119371, 2007-0128862, 2007-0128863, and 2007-0128864, which arehereby incorporated by reference in their entirety. In anotherembodiment, a chamber configured to operate in both an ALD mode as wellas a conventional CVD mode may be used to deposit cobalt-containingmaterials is described in commonly assigned U.S. Pat. No. 7,204,886,which is incorporated herein by reference in its entirety. A detaileddescription of an ALD process for forming cobalt-containing materials isfurther disclosed in commonly assigned U.S. Pat. Nos. 7,264,846 and7,404,985, which are hereby incorporated by reference in their entirety.In other embodiments, a chamber configured to operate in both an ALDmode as well as a conventional CVD mode that may be used to depositcobalt-containing materials is the TXZ® showerhead and CVD chamberavailable from Applied Materials, Inc., located in Santa Clara, Calif.An example of a suitable vapor deposition chamber includes the WXZ™ CVDchamber, commercially available from Applied Materials, Inc., located inSanta Clara, Calif. The vapor deposition chamber may be adapted todeposit materials by conventional CVD, pulsed-CVD, or PE-CVD techniquesas well as by ALD and PE-ALD techniques. Also, the vapor depositionchamber may be used as for treatment processes, such as an in situplasma process, a remote plasma process, or a thermal annealing process.

“Substrate surface” or “substrate,” as used herein, refers to anysubstrate or material surface formed on a substrate upon which filmprocessing is performed during a fabrication process. For example, asubstrate surface on which processing may be performed include materialssuch as monocrystalline, polycrystalline or amorphous silicon, strainedsilicon, silicon on insulator (SOI), doped silicon, silicon germanium,germanium, gallium arsenide, glass, sapphire, silicon oxide, siliconnitride, silicon oxynitride, and/or carbon doped silicon oxides, such asSiO_(x)C_(y), for example, BLACK DIAMOND® low-k dielectric, availablefrom Applied Materials, Inc., located in Santa Clara, Calif. Substratesmay have various dimensions, such as 100 mm, 200 mm, 300 mm, or 450 mmdiameter wafers, as well as, rectangular or square panes. Unlessotherwise noted, embodiments and examples described herein are usuallyconducted on substrates with a 200 mm diameter or a 300 mm diameter,more preferably, a 300 mm diameter. Processes of the embodimentsdescribed herein may be used to deposit cobalt materials (e.g., metalliccobalt) on many substrates and surfaces, especially, barrier layers andlayers. Substrates on which embodiments of the invention may be usefulinclude, but are not limited to semiconductor wafers, such ascrystalline silicon (e.g., Si<100> or Si<111>), silicon oxide, strainedsilicon, silicon germanium, doped or undoped polysilicon, doped orundoped silicon wafers, and patterned or non-patterned wafers.Substrates may be exposed to a pre-treatment process to polish, etch,reduce, oxidize, hydroxylate, heat, and/or anneal the substrate orsubstrate surface.

While the foregoing is directed to embodiments of the invention, otherand further embodiments of the invention may be devised withoutdeparting from the basic scope thereof, and the scope thereof isdetermined by the claims that follow.

The invention claimed is:
 1. A method for depositing materials on asubstrate surface, comprising: forming a barrier layer on a substrate,wherein the barrier layer comprises a metallic layer, a metal nitridelayer, or combinations thereof; exposing the substrate to dicobalthexacarbonyl butylacetylene (CCTBA) and hydrogen to form a cobalt layeron the barrier layer during a vapor deposition process; and depositing aconductive material over the cobalt layer, wherein the cobalt layer ismetallic cobalt, cobalt boride, cobalt phosphide, or combinationsthereof.
 2. The method of claim 1, further comprising exposing thebarrier layer or the cobalt layer to a plasma during a treatmentprocess, wherein the plasma is formed from nitrogen (N₂), ammonia (NH₃),hydrogen (H₂), or combinations thereof.
 3. The method of claim 2,wherein the barrier layer or the cobalt layer is exposed to a hydrogenplasma for a time period within a range from about 20 seconds to about40 seconds and the hydrogen plasma is formed by a remote plasma source.4. The method of claim 1, further comprising exposing the barrier layeror the cobalt layer to a gas during a thermal treatment process, whereinthe gas is nitrogen (N₂), ammonia (NH₃), hydrogen (H₂), or combinationsthereof.
 5. The method of claim 4, wherein the substrate is heated to atemperature within a range from about 50° C. to about 400° C. during thethermal treatment process.
 6. The method of claim 1, wherein thesubstrate is exposed to a deposition gas comprising the CCTBA and thehydrogen during a thermal chemical vapor deposition process.
 7. Themethod of claim 6, wherein the substrate is heated to a temperaturewithin a range from about 100° C. to about 250° C. during the thermalchemical vapor deposition process.
 8. The method of claim 1, wherein thesubstrate is sequentially exposed to the CCTBA and the hydrogen duringan atomic layer deposition process.
 9. The method of claim 1, whereinthe barrier layer is tantalum, tantalum nitride, titanium, titaniumnitride, tungsten, tungsten nitride, alloys thereof, derivativesthereof, or combinations thereof.
 10. The method of claim 9, wherein thebarrier layer is a tantalum nitride layer disposed on a tantalum layer.11. The method of claim 1, wherein the conductive material comprisescopper or a copper alloy.
 12. The method of claim 11, wherein theconductive material comprises a seed layer and a bulk layer.
 13. Themethod of claim 12, wherein the seed layer comprises copper and isdeposited by a physical vapor deposition process or a chemical vapordeposition process.
 14. The method of claim 12, wherein the bulk layercomprises copper and is deposited by an electrochemical plating process.15. The method of claim 11, wherein the conductive material is directlydeposited on the cobalt layer by an electrochemical plating process. 16.A method for depositing materials on a substrate surface, comprising:forming a barrier layer on a substrate, wherein the barrier layer is ametallic layer, a metal nitride layer, or combinations thereof; exposingthe substrate to dicobalt hexacarbonyl butylacetylene (CCTBA) andhydrogen to form a cobalt layer on the barrier layer during a vapordeposition process; exposing the cobalt layer to a plasma during apost-treatment process; and depositing a copper layer on the cobaltlayer by a vapor deposition process, wherein the cobalt layer ismetallic cobalt, cobalt boride, cobalt phosphide, or combinationsthereof.
 17. The method of claim 16, wherein the plasma is formed fromnitrogen (N₂), ammonia (NH₃), hydrogen (H₂), argon, helium, orcombinations thereof.
 18. The method of claim 17, wherein the cobaltlayer is exposed to the plasma for a time period within a range fromabout 20 seconds to about 40 seconds, and the plasma is formed by aremote plasma source.
 19. The method of claim 16, wherein the substrateis exposed to a deposition gas comprising the CCTBA and the hydrogenduring a thermal chemical vapor deposition process.
 20. The method ofclaim 19, wherein the substrate is heated to a temperature within arange from about 100° C. to about 250° C. during the thermal chemicalvapor deposition process.
 21. The method of claim 16, wherein thesubstrate is sequentially exposed to the CCTBA and the hydrogen duringan atomic layer deposition process.
 22. The method of claim 16, whereinthe cobalt layer is formed during a plasma-enhanced chemical vapordeposition process or a plasma-enhanced atomic layer deposition process.23. The method of claim 16, wherein the barrier layer is tantalum,tantalum nitride, titanium, titanium nitride, tungsten, tungstennitride, alloys thereof, derivatives thereof, or combinations thereof.24. The method of claim 23, wherein the barrier layer is a tantalumnitride layer disposed on a tantalum layer.
 25. A method for depositingmaterials on a substrate surface, comprising: forming a barrier layer ona substrate, wherein the barrier layer is selected from the groupconsisting of tantalum, tantalum nitride, titanium, titanium nitride,tungsten, tungsten nitride, alloys thereof, derivatives thereof, andcombinations thereof; exposing the substrate to dicobalt hexacarbonylbutylacetylene (CCTBA) and a reducing gas to form a cobalt layer on thebarrier layer during a vapor deposition process; exposing the cobaltlayer to a hydrogen plasma during a post-treatment process; anddepositing a copper material over the cobalt layer, wherein the cobaltlayer is metallic cobalt, cobalt boride, cobalt phosphide, orcombinations thereof.